Abstract
Gently warming the η6,η5-bis(indenyl)zirconium dimethoxyethane compound (η6-C9H5-1,3-(SiMe3)2)(η5-C9H5-1,3-(SiMe3)2)Zr(DME) (1-DME) to 45 °C resulted in C−O bond scission to yield an equimolar mixture of the zirconocene ethylene compound (η5-C9H5-1,3-(SiMe3)2)2Zr(η2-CH2CH2) and the corresponding zirconium bis(methoxide) complex (η5-C9H5-1,3-(SiMe3)2)2Zr(OMe)2. Monitoring the relative rates of 1-DME versus 1-DME-d10 cleavage by 1H NMR spectroscopy established no kinetic isotope effect (kH/kD = 1.0(1)), eliminating the possibility of C−H activation in or prior to the rate-determining step. Computational studies support a pathway involving rate-determining DME dissociation from the η6,η5-bis(indenyl)zirconium complex followed by facile η6 to η5 indenyl haptotropic rearrangement and C−O bond scission. Corresponding C−S bond cleavage chemistry has been investigated for three thioethers and the mechanism of bond activation compared to the oxygen congeners.
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